Fuel with low sulphur content for diesel engines

ABSTRACT

The invention concerns a fuel for diesel engines, with a sulphur content of less than 500 ppm containing in a major proportion at least one average distillate from a straight-run distilling cup of crude oil, with temperature ranges between 150 and 400° C. and in a minor proportion a lubricating additive containing monocarboxylic and polycyclic acids. The said fuel is characterized in that it contains at least 20 ppm of the additive consisting of at least one monocarboxylic aliphatic hydrocarbon, saturated or unsaturate, of linear chain between 12 and 14 carbon atoms, and at least one polcyclic hydrocarbon compound, containing at least two cycles each formed of 5 to 6 atoms one of which at most is optionally a heteroatom such as nitrogen or oxygen and the other atoms are carbon atoms, these two cycles having further two carbon atoms in common, preferably vicinal, these said cycles being saturated or unsaturated, substituted or non-substituted by at least one single grouping selected among the carboxylic, amine carboxyl, ester and nitrile groupings, the fuel containing more than 60 ppm of additive when the said combination is tall oil.

[0001] The present invention relates to a fuel containing a lubricity additive for improving the lubricating properties of fuels, regardless of whether diesel fuel or jet fuel is involved, and more particularly of diesel fuels with a low sulphur content.

[0002] It is well known that diesel fuels and jet fuels must be capable of lubrication, for the protection of pumps, injection systems and of all the moving parts with which these products come into contact in an internal combustion engine. With the intention of employing products which are increasingly pure and nonpolluting, especially devoid of sulphur, the refining industry has been led increasingly to improve its treatment processes for the removal of sulphur compounds. However, it was noticed that, when losing the sulphur compounds, the aromatic and polar compounds, often associated, were also being lost, and this resulted in a loss of the lubricating power of these fuels. Thus, beyond certain contents, the elimination of sulphur compounds from the composition of these products very substantially promotes the phenomena of wear and of failure of moving components where pumps and injection systems are concerned. As in many countries the regulations have imposed a limitation on the acceptable upper content of sulphur compounds in fuels to 0.05% by weight, in order to lower the emissions of polluting combustion gases from cars, lorries and buses, especially in urban built-up areas, these lubricating compounds must be replaced with other compounds which are nonpolluting with regard to the environment but exhibit a sufficient lubricating power to avoid the risks of wear.

[0003] A number of types of additives have already been proposed in order to solve this problem. Antiwear additives have thus been added to diesel fuels, some of these being known in the field of lubricants, of the type of fatty acid esters and of unsaturated fatty acid dimers, aliphatic amines, esters of fatty acids and of diethanolamine and long-chain aliphatic monocarboxylic acids, as described in U.S. Pat. Nos. 2,252,889, 4,185,594, 4,204,481, 4,208,190 and 4,428,182. Most of these additives exhibit a sufficient lubricating power, but in concentrations which are much too high, and this is economically highly disadvantageous for purchase. Moreover, additives containing acid dimers, like those containing acid trimers, cannot be employed in fuels fed to vehicles in which the fuel may be in contact with the lubricating oil, because these acids form, by chemical reaction, deposits which are sometimes insoluble in the oil but, above all, incompatible with the detergents usually employed.

[0004] U.S. Pat. No. 4,609,376 recommends the use of antiwear additives obtained from esters of mono- and polycarboxylic acids and polyhydroxylated alcohols in fuels containing alcohols in their composition.

[0005] U.S. Pat. No. 2,686,713 recommends the introduction of tall oil up to 60 ppm in diesel fuels in order to prevent rust formation on metal surfaces in contact with these fuels.

[0006] Another chosen route is to introduce vegetable oil esters or vegetable oils themselves into these fuels, to improve their lubricating power or their lubricity. These include esters derived from rapeseed, linseed, soya and sunflower oils or the oils themselves (see patents EP 635,558 and EP 605,857). One of the major disadvantages of these esters is their low lubricating power at a concentration lower than 0.5% by weight in the fuels.

[0007] To improve the lubricating power of diesel fuels, patent application WO 95/33805 recommends the introduction of a cold-resistance additive consisting of nitrogenous additives containing one or more >N—R¹³ groups in which R¹³ contains from 12 to 24 carbon atoms, is linear, slightly branched or alicyclic and aromatic, it being possible for the nitrogenous group to be linked via CO or CO₂ and to form amine carboxylates or amides.

[0008] The present invention aims to solve the problems encountered with the additives proposed by the prior art, that is to say to improve the lubricating power of the desulphurized and dearomatized fuels, while they remain compatible with the other additives, especially detergents, and the lubricating oils, especially in not forming deposits and in reducing the cost, especially owing to a lower additive content, markedly lower than 0.5%.

[0009] The subject-matter of the present invention is a diesel engine fuel with a sulphur content lower than 500 ppm, including a major portion of at least one middle distillate originating from a direct distillation cut of crude oil, at temperatures of between 150 and 400° C. and a minor portion of a lubricity additive containing monocarboxylic and polycyclic acids, the said fuel being characterized in that it contains at least 20 ppm of the additive consisting of a combination of at least one saturated or unsaturated, monocarboxylic aliphatic hydrocarbon with a linear chain of between 12 and 24 carbon atoms, and of at least one polycyclic hydrocarbon compound containing at least two rings, each formed by 5 to 6 atoms of which at most one is optionally a heteroatom such as nitrogen or oxygen and the others are carbon atoms, these two rings additionally having two, preferably vicinal, carbon atoms in common, these said rings being saturated or unsaturated, unsubstituted or substituted by at least one single group chosen from the group made up of carboxylic, amine carboxylate, ester and nitrile groups, the fuel containing more than 60 ppm of additive when the said combination is tall oil.

[0010] It has been noticed that the lubricating power introduced by the lubricity additive containing such a combination is well superior to that foreseeable on adding the lubricating powers of each of its components taken separately. This unforeseeable result expresses the synergistic effect of the various components of the said composition with regard to lubrication.

[0011] According to a first embodiment of the fuel according to the invention the polycyclic hydrocarbon compound of the said combination is a hydrocarbon compound of formula (I) below:

[0012] with X denoting the atoms of each ring corresponding to 4 carbons, or 3 carbons and a heteroatom such as nitrogen or oxygen, with R₁, R₂, R₃ and R₄, which are identical or different, denoting either a hydrogen atom or hydrocarbon groups, each connected to at least one atom of one of the two rings, these hydrocarbon groups being chosen from alkyl groups consisting of 1 to 5 carbon atoms, aryl groups, hydrocarbon rings of 5 to 6 atoms, optionally containing a heteroatom such as oxygen or nitrogen, each ring being formed by direct connection of two groups R_(i) chosen from R₁, R₂, R₃ and R₄, optionally via a heteroatom, the said ring being saturated or unsaturated, unsubstituted or substituted by an optionally olefinic, aliphatic radical containing from 1 to 4 carbon atoms, and Z is chosen from the group consisting of carboxylic groups, amine carboxylates, esters and nitrites.

[0013] In a particular version of this first embodiment, the compound of formula (I) is chosen from the group consisting of the natural resin-based acids obtained from residues of distillation of natural oils extracted from resinous trees, especially resinous conifers, and the amine carboxylates, esters and nitriles of these acids.

[0014] Among the resin-based acids preference is given to abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, laevopimaric acid and parastrinic acid and their derivatives.

[0015] In a second embodiment of the invention, the polycyclic hydrocarbon compound of the said combination is a hydrocarbon compound of formula (II) below;

[0016] in which at most one X of each ring is a heteroatom such as nitrogen or oxygen, the other Xs being carbon atoms, in which R₁, R₂, R₃ and R₄, which are identical or different, are either a hydrogen atom or hydrocarbon groups, each connected to at least one atom of one of the two rings, these hydrocarbon groups being chosen from alkyl groups containing from 1 to 5 atoms, aryl groups, hydrocarbon rings of 5 to 6 atoms, optionally containing a heteroatom such as oxygen or nitrogen, each ring being formed by direct connection of two groups R_(i) chosen from R₁, R₂, R₃ and R₄, optionally via a heteroatom, the said ring being saturated or unsaturated, unsubstituted or substituted by an optionally olefinic aliphatic radical containing from 1 to 4 carbon atoms, and Z, connected to at least one atom of at least one of the two rings, is chosen from the group consisting of carboxylic groups, amine carboxylates, esters and nitrites.

[0017] According to the invention the monocarboxylic aliphatic hydrocarbon is in the form of acid, of amine carboxylate and of esters.

[0018] In a more advanced version of the invention, the combination includes from 1 to 50% by weight of at least one compound corresponding to at least one of the formulae (I) and (II) and from 50 to 99% by weight of at least one saturated or unsaturated, linear monocarboxylic acid containing from 12 to 24 carbon atoms, these products being present in the form of acid, of amine carboxylate or of esters.

[0019] Amine carboxylates are intended to mean compounds resulting from the reaction of these acids with primary, secondary and tertiary amines or polyamines containing from 1 to 8 carbon atoms per chain and primary, secondary or tertiary alkyleneamines and alkylenepolyamines containing from 2 to 8 carbon atoms. In a preferred version of the invention these amine salts are derived from mines chosen from the group consisting of 2-ethyl-hexylamine, N,N-dibutylamine, ethylenediamine, diethylenetriamine and tetraethylenepentamine.

[0020] Among the esters preference is given to esters of primary alkanols containing from 1 to 8 carbon atoms or else polyalcohols of the group consisting of ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, diethanolamine, triethanolamine and their derivatives.

[0021] In a preferred version of the invention the fuel contains from 50 to 1000 ppm of the lubricity additive.

[0022] According to the present invention at least one additive from the group of the additives usually added to such fuels may be added to the said fuel, such as detergent additives, additives which improve the cetane number, deemulsifying additives, anticorrosion additives, additives which improve resistance to cold and odour-modifying additives.

[0023] To clarify the advantages of the present invention in comparison with the prior art, examples are given below by way of illustration but without limiting the scope of the invention claimed.

EXAMPLE I

[0024] This example describes the choice of the additives as a function of their solubility in a low-sulphur diesel fuel.

[0025] Each test additive is diluted to 5% by weight in a diesel fuel (DF) containing 500 ppm of sulphur, at ambient temperature.

[0026] In Table I, below, the additives according to the invention are denoted by Y and the comparative examples by C. The additives Y consist partly of a mixture of a combination of fatty acids containing, by weight, 50 to 55% of oleic acid, 30 to 40% of linolenic acid, 3 to 5% of palmitic acid and 1 to 2% of linolenic acid, and partly of resin-based acids obtained by distillation of tall oil, a by-product of manufacture of wood pulp by the sulphate process. In the case of the comparative examples, C₁ corresponds to pure oleic acid, C₂ to rosin, which is a mixture of resin-based acids corresponding to the residue from distillation of pine resins, and C₃ is a mixture of acid dimers obtained by thermal and/or catalytic dimerization of unsaturated fatty acids. TABLE I % Fatty % Resin-based Additive acids acids Solubility in DF Y₁ 70 30 soluble Y₂ 85 15 soluble Y₃ 98 2 soluble C₁ 100 0 soluble C₂ 0 100 very cloudy C₃ 0 0 soluble

[0027] From this table it is found that, with the exception of the resin-based acids (C₂), all these compounds are very soluble in diesel fuel.

EXAMPLE II

[0028] This example examines the lubricating power of the additives described in Example I.

[0029] The lubricating power of these additives was measured in the conditions of the HFRR (High Frequency Reciprocating Rig) test as described in the SAE paper 932692 by J. W. Hadley of Liverpool University.

[0030] The test consists in applying to a steel ball in contact with a motionless metal plate a pressure corresponding to a weight of 200 g conjointly with an alternating movement of 1 mm at a frequency of 50 Hz. The moving ball is lubricated by the composition being tested. The temperature is maintained at 60° C. throughout the test period, that is to say 75 min. The lubricating power is expressed by the mean value of the diameters of the wear imprint of the ball on the plate. A small wear diameter (generally smaller than 400 μm) indicates a good lubricating power; conversely, a large wear diameter (greater than 400 μm) expresses a power which is proportionately more insufficient the larger the value of the wear diameter.

[0031] The lubricating power of the additives was measured on a diesel fuel identical with that of Example I, each test sample containing only 100 ppm of additive. The results are given in Table II below. TABLE II Wear diameter Sample (μm) Diesel fuel alone 510 (DF) DF + Y₁ 350 DF + Y₂ 385 DF + Y₃ 410 DF + C₁ 440 DF + C₂ 470 DF + C₃ 380

[0032] This table shows that the additives (Y₁ and Y₂) according to the invention have an identical or even better effect than the acid dimers (C₃). In addition, it is found that the mixture of fatty acids with resin-based acids has a lubricating power which is much better than those obtained with these same compounds taken separately, expressing a mutual synergism of these components.

EXAMPLE III

[0033] This example examines the compatibility of the additives described in Example I with the lubricants usually employed in diesel engines, according to the procedure described below.

[0034] 70 ml of an engine oil of total basicity equal to 15 mg of KOH per gram are mixed with 700 ml of diesel fuel containing 500 ppm of sulphur, identical with that of Example I, to which 35 g of additive are added. Each mixture thus formed is placed in an oven at 50° C. and then a visual assessment is made of the presence or the absence of deposits, of a precipitate or of cloudiness resulting from an incompatibility between the so-called “lubricity” additives, of sufficient lubricating power, with an engine lubricant called KM2+ marketed by the Renault Diesel Oils Company.

[0035] The compatibility results are collated in Table III below. TABLE III Additive Compatibility with the lubricant Y₁ No deposit - clear solution Y₂ No deposit - clear solution Y₃ No deposit - very slight turbidity C₁ Very slight cloudiness after 48 hours C₂ Presence of a few insolubles C₃ Formation of cloudiness as soon as DF containing additive is added

[0036] The additives of the invention, Y₁ and Y₂, give neither any deposit nor cloudiness when the diesel fuel containing 100 ppm of additive is added to the oil.

EXAMPLE IV

[0037] This example aims to describe the lubricity additives suitable for being introduced into the fuels according to the invention.

[0038] These are, on the one hand, esters obtained by reacting alcohols with the additive Y₁ of Example I in an equimolar mixture, in maintaining this mixture at reflux between 130 and 150° C. at atmospheric pressure, and in then distilling the water/toluene azeotrope.

[0039] On the other hand, they are amine carboxylates obtained merely by mixing, at ambient temperature and at atmospheric pressure, Y₁ with an amine or polyamine according to the invention, thus permitting the neutralization of the carboxylic sites.

[0040] These additives are introduced into a diesel fuel such as that described in Example II, at a concentration of 100 ppm.

[0041] Table IV collates below the results of the wear test described in Example II, which are obtained with the diesel fuel doped in this way, to characterize their lubricating power. TABLE IV Nature of the additive Wear diameter (Y1 + etc.) (μm) triethanolamine 365 N,N-dimethylethanolamine 375 ethylene glycol 385 glycerol 360 propylene glycol 380 2-ethylhexanol 385 N,N-dimethyl-1,3- 360 propylenediamine 2-ethylhexylamine 370 N,N-dibutylamine 375 ethylenediamine 355

[0042] According to these results it is confirmed that the fuels doped with such additives according to the invention have a good lubricating power. 

1. Diesel engine fuel with a sulphur content lower than 500 ppm, including a major portion of at least one middle distillate originating from a direct distillation cut of crude oil, at temperatures of between 150 and 400° C. and a minor portion of a lubricity additive containing monocarboxylic and polycyclic acids, the said fuel being characterized in that it contains at least 20 ppm of the additive consisting of a combination of at least one saturated or unsaturated, monocarboxylic aliphatic hydrocarbon with a linear chain of between 12 and 24 carbon atoms, and of at least one polycyclic hydrocarbon compound containing at least two rings, each formed by 5 to 6 atoms of which at most one is optionally a heteroatom such as nitrogen or oxygen and the others are carbon atoms, these two rings additionally having two, preferably vicinal, carbon atoms in common, these said rings being saturated or unsaturated, unsubstituted or substituted by at least one single group chosen from carboxylic, amine carboxylate, ester and nitrile groups, the fuel containing more than 60 ppm of additive when the said combination is tall oil.
 2. Fuel according to claim 1, characterized in that the polycyclic hydrocarbon compound of the said combination is a hydrocarbon compound of formula (I) below:

with X denoting the atoms of each ring corresponding to 4 carbons, or 3 carbons and a heteroatom such as nitrogen or oxygen, with R₁, R₂, R₃ and R₄, which are identical or different, denoting either a hydrogen atom or hydrocarbon groups, each connected to at least one atom of one of the two rings, these hydrocarbon groups being chosen from alkyl groups consisting of 1 to 5 carbon atoms, aryl groups, hydrocarbon rings of 5 to 6 atoms, optionally containing a heteroatom such as oxygen or nitrogen, each ring being formed by direct connection of two groups R_(i) chosen from R₁, R₂, R₃ and R₄, optionally via a heteroatom, the said ring being saturated or unsaturated, unsubstituted or substituted by an optionally olefinic, aliphatic radical containing from 1 to 4 carbon atoms, and Z is chosen from the group consisting of carboxylic, amine carboxylate, ester and nitrile groups.
 3. Fuel according to either of claims 1 and 2, characterized in that the compound of formula (I) is chosen from the group consisting of the natural resin-based acids obtained from residues of distillation of natural oils extracted from resinous trees, especially resinous conifers, the amine carboxylates and the ester and nitrile derivatives of these acids.
 4. Fuel according to one of claims 1 to 3, characterized in that the resin-based acids are chosen from the group consisting of abietic acid, dihydroabietic acid, tetrahydroabietic acid, dehydroabietic acid, neoabietic acid, pimaric acid, laevopimaric acid, parastrinic acid and their derivatives.
 5. Fuel according to claim 1, characterized in that the polycyclic hydrocarbon compound is a hydrocarbon compound of formula (II) below:

in which at most one X of each ring is a heteroatom such as nitrogen or oxygen, the other Xs being carbon atoms, in which R₁, R₂, R₃ and R₄, which are identical or different, correspond to a hydrogen atom or hydrocarbon groups, each connected to at least one atom of one of the two rings, these hydrocarbon groups being chosen from alkyl groups containing from 1 to 5 atoms, aryl groups, hydrocarbon rings of 5 to 6 atoms, optionally containing a heteroatom such as oxygen or nitrogen, each ring being formed by direct connection of two groups R_(i) chosen from R₁, R₂, R₃ and R₄, optionally via a heteroatom, the said ring being saturated or unsaturated, unsubstituted or substituted by an optionally olefinic aliphatic radical containing from 1 to 4 carbon atoms, and Z, connected to at least one atom of at least one of the two rings, is chosen from the group consisting of carboxylic, amine carboxylate, ester and nitrile groups.
 6. Fuel according to one of claims 1 to 5, characterized in that the monocarboxylic aliphatic hydrocarbon is in the form of acid, of amine carboxylate and/or of esters.
 7. Fuel according to one of claims 1 to 6, characterized in that it includes from 1 to 50% by weight of at least one compound corresponding to at least one of the formulae (I) and (II), and from 50 to 90% by weight of at least one saturated or unsaturated, linear monocarboxylic aliphatic hydrocarbon containing from 12 to 24 carbon atoms.
 8. Fuel according to one of claims 1 to 7, characterized in that the amine carboxylates result from the reaction of these acids with primary, secondary and tertiary amines or polyamines containing from 1 to 8 carbon atoms per chain and primary, secondary or tertiary alkyleneamines and alkylenepolyamines containing from 2 to 8 carbon atoms.
 9. Fuel according to claim 8, characterized in that the amines from which the amine carboxylates are derived are chosen from the group consisting of 2-ethylhexyl-amine, N,N-dibutylamine, ethylenediamine, diethylene-triamine and tetraethylenepentamine.
 10. Fuel according to one of claims 1 to 7, characterized in that the esters result from the reaction of these acids with alcohols of the group consisting of the primary alcohols containing from 1 to 8 carbon atoms and polyalcohols of the ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, diethanolamine and triethanolamine type.
 11. Fuel according to one of claims 1 to 10, characterized in that it contains from 50 to 1000 ppm of a lubricity additive. 